Hydrovinylation Reactions – Atom‐Economic Transformations with Steadily Increasing Synthetic Potential

Hilt, Gerhard

doi:10.1002/ejoc.201200212

Cited by 107 publications

(65 citation statements)

References 104 publications

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“…In these experiments, 6 carried out using cobalt (II) chloride-complexes of 1,n- bis -diphenylphosphinoalkane ligands and various promoters, we recognized that trimethylaluminum, a Lewis acidic alkylating agent which we had successfully used previously 7 gave unacceptable yields of the expected hydrovinylation product ( 9a ). Alternate procedures using Zn/ZnI 2 in place of the aluminum reagents 8 also gave unsatisfactory results.…”

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confidence: 99%

Asymmetric Catalysis with Ethylene. Synthesis of Functionalized Chiral Enolates

et al. 2015

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Trialkylsilyl enol ethers are versatile intermediates often used as enolate surrogates for the synthesis of carbonyl compounds. Yet there are no reports of broadly applicable, catalytic methods for the synthesis of chiral silyl enol ethers carrying latent functionalities useful for synthetic operations beyond the many possible reactions of the silyl enol ether moiety itself. Here we report a general procedure for highly catalytic (substrate:catalyst ratio up to 1000:1) and enantioselective (92% to 98% major enantiomer) synthesis of such compounds bearing a vinyl group at a chiral carbon at the β-position. The reactions, run under ambient conditions, use trialkylsiloxy-1,3-dienes and ethylene (1 atmosphere) as precursors, and readily available (bis-phosphine)-cobalt(II) complexes as catalysts. The silyl enolates can be readily converted into novel enantiopure vinyl triflates, a class of highly versatile cross-coupling reagents, enabling the syntheses of other enantiomerically pure, stereo-defined trisubstituted alkene intermediates not easily accessible by current methods. Examples of Kumada, Stille and Suzuki coupling reactions are illustrated.

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confidence: 99%

Asymmetric Catalysis with Ethylene. Synthesis of Functionalized Chiral Enolates

et al. 2015

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“…Codimerization of ethylene with various vinyl monomers (hydrovinylation) has been known [157,158]. The catalyst for the hydrovinylation involves Ni, Pd, and Ru.…”

Section: Cooligomerization Of Other Vinyl Monomersmentioning

confidence: 99%

Oligomerization of Olefins

Takeuchi

Osakada

2014

Organometallic Reactions and Polymerization

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This article reviews recent studies on oligomerization of olefins catalyzed by transition metal complexes. Ni, Pd, and Fe complexes, having a ligand with a similar structure to the ethylene polymerization catalyst but with less bulky substituents, convert ethylene to the oligomers as a mixture with various chain lengths with Schulz-Flory molecular weight distribution. Cossee-type insertion of ethylene into the M-C bond and frequent elimination of a-olefins are proposed as the major reaction mechanism. The reaction using the Fe catalyst for polymerization and large excess of chain transfer reagents such as ZnEt 2 can yield the oligomers with Poisson distribution. Cr complexes with various ligands promote selective trimerization and/or tetramerization of ethylene to produce 1-hexene and/ or 1-octene. The mechanism involving metallacycle is proposed to account for the selectivity. Several Ti and Ta complexes are also effective for the trimerization of ethylene. Oligomerization of a-olefins has been also studied, although the product is frequently composed of branched oligomers and/or inner olefins.

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“…[113] The product obtained from alkene hydrovinylation is also an alkene, and thus selectivity for the reaction between the substrates, and not with the product, is often the most significant factor in determining the efficiency of a given process. Repeated hydrovinylation of the alkene product would lead to a polymerisation reaction.…”

Section: Hydrovinylationmentioning

confidence: 99%

Iron‐Catalysed Hydrofunctionalisation of Alkenes and Alkynes

2014

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The metal‐catalysed hydrofunctionalisation of alkenes and alkynes provides a convenient and atom‐economic route to diversely functionalised products with control of regio‐, chemo‐ and stereoselectivity. As one of the most abundant elements on earth, iron offers a level of sustainable and long‐term availability that is uncommon for most transition metals. Although iron is commonly found in the oxidation states of +2 and +3, the use of redox‐active ligands has allowed the synthesis and application of low oxidation state iron complexes in catalysis. A broad range of hydrofunctionalisation reactions have been developed by using iron catalysts in a wide variety of oxidation states. Intense development over the past decade has resulted in the development of iron‐catalysed hydroamination, hydroalkoxylation, hydrocarboxylation, hydrothiolation, hydrovinylation, hydrosilylation, hydroboration, hydrophosphination, hydromagnesiation and carbonylation reactions, amongst others. With the field still in its infancy, there is great potential for further developments in the mechanistic understanding and synthetic and industrial applicability of these processes.

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Hydrovinylation Reactions – Atom‐Economic Transformations with Steadily Increasing Synthetic Potential

Cited by 107 publications

References 104 publications

Asymmetric Catalysis with Ethylene. Synthesis of Functionalized Chiral Enolates

Asymmetric Catalysis with Ethylene. Synthesis of Functionalized Chiral Enolates

Oligomerization of Olefins

Iron‐Catalysed Hydrofunctionalisation of Alkenes and Alkynes

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